Process for removing trace metals with hydrogen and an inert packing material



2,91 0,434l OGEN Oct. 27, 1959 H. v. Hass ETAI- PROCESS FOR REMOVING TRACE METALS WITH HYDR AND AN INERT PACKING MATERIAL Filed nay 24, 1955 1115, 1 tlinx,

United States Patent() M' PRGCESS FOR REMOVING TRACE METALS WITH HYDROGEN AND AN lNERT PACKING MATERIAL Howard V. Hess, Glenham, Jack Ryer, Wappingers Falls, and Marc Fontaine, Fishkill, N .Y., assgnors to Texaco Inc., a corporation of Delaware Application May 24, 1955, Serial No. 510,628

8 Claims. (Cl. 208-251) This invention is concerned with the treatment of petroleum crude oils and residual oils to elfect the removal of trace metal components.

It has long been known that various metallic elements are found in naturally occurring petroleum crude oils. Among the metallic Velements which have been found in crude oils are: iron, nickel, vanadium, aluminum, sodium, copper, calcium, magnesium, manganese, barium, silicon, chromium, tin, lead, molybdenum, strontium, cobolt, beryllium, lithium, rubidium, silver, bismuth, titanium, zinc, potassium, and gold.1 In addition to naturally occurring metals, extraneous metals may be introduced in the rening of crude oils and appear in the residual oils from crude oil distillation.

Some of these metals are known to be harmful when included in charge stocks for further refining. In catalytic cracking, the presence of minute amounts of heavy metals, for example, iron, nickel, vanadium and copper in the charge stock causes greatly increased gas and coke yields `and reduced gasoline production. Some of these metals, particularly nickel and vanadium, have been found to be undesirable in fuels for boilers and combustion turbines. In the case of boiler fuels, these metals accelerate the deterioration of the common refractory materials. In the case of combustion turbines, these metals accelerate corrosion, and failure of the turbine blades.

Because of the harmful effects of trace metal components of crude and residual oils, these oils have usually been considered unsatisfactory for inclusion in the charge Vto catalytic cracking facilities. One method of preparing catalytic cracking feed stocks from such metalcontaining oils` has been to use low pressure distillation to separate a distillate charge stock. However, when high yields of distillate are obtained, trace metals are frequently found in the distillates in objectionable quantities. Although some of these metals may be introduced into the distillate by mechanical entrainment, it appears that the naturally occurring metals are present in the form of metallo-organic compounds of significant vapor `pressure and are distilled with the oil.

This invention provides a means by which crude oils, residual oils, and other contaminated oils may be treated to render them satisfactory for inclusion in catalytic cracking charge stock, boiler fuels, turbine fuels, or for other applications Where trace metallic components are undesirable. In the method of this invention, the oil lMllner, O. I., Glass, I. R., Kirchner, J. P., Yuriclr, A. N., Anal. Chem., 24, 1728 (1952).

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to be treated is contacted with hydrogen under conditions such that at least a portion of the hydrogen is reacted with a component of the oil to produce an oil of increased API gravity and reduced trace metal content, and a solid residue incorporating trace metals. The treated oil is then separated from the metal-containing solid residue. The solid residue may be further processed to recover the metals contained therein.

An advantage of this process is that it provides a method of separating trace metal components from crude petroleum oils, residual oils, and other oils containing metallic contaminants.

A further advantage of this process is that it converts oils of low quality to useful stocks suitable for inclusion in catalytic cracking charge stocks, boiler fuels, and combustion turbine fuels.

Another advantage of this process is that valuable trace metals contained in many oils may be removed in the form of a solid residue. This residue may be further processed to recover the valuable metals contained therein.

The accompanying figures diagrammatically illustrate the process of our invention, Although the drawings are illustrative of embodiments in which the process of this invention may be practiced, it is not intended to limit the invention to the particular apparatus or materials described.

Figure l is a flow diagram of one embodiment of the invention. Figure 2 is a flow diagram of another ernbodimentV of the invention. Referring to Figure l, a trace metal-containing oil to be treated is Withdrawn from external storage, not shown, and admitted to the system through line 1. Hydrogen or a. hydrogen-containing gas from an external source, not shown, is charged through line 2, admixed with the oil in line 1 and the combined stream is directed through line 3 to heated reaction coil 4. In heated reaction coil 4 the oil and hydrogen are raised to a temperature at which hydrogen reacts at a reasonably rapid rate with a component of the oil. Efliuent from reaction coil 4 passes through line 5, cooler 6, line 7 and is discharged into gas-liquid separator 8. Unreacted hydrogen or hydrogen-containing gas is Withdrawn from separator 8 through line 9 and discharged from the system. The liquid phase separated in gas-liquid separator 8 comprises a solid residue dispersed in treated oil. This dispersion or suspension is Withdrawn from separator 8 through line 10 and directed to filter 11. The solid residue containing trace metals is` separated from the treated oil in filter 11, the treated oil Withdrawn through line 12 and discharged to external tankage, not shown. The separated metal-containing solid residue from filter 11 is Withdrawn by solids handling facilities indicated as line 13 and is transferred to external storage,.not shown.

Several modifications of this invention are shown in Figure 2. Referring to Figure 2, a trace metalcontaining oil is Withdrawn through line 20 from an external source, not shown and is fed to the system by charge pump 21. Hydrogen-containing recycle gas in line 22 is adrnixed with the oil discharged from pump 21 and transferred through line 23 to heater 24. Heater 24 is used to bring the oil and hydrogen to a temperature at which hydrogen will react rapidly with a component of the oil. The

heater eluent is then transferred through line 25 to soaking drum 26 which provides additional time for reaction between the oil and hydrogen. Soaking drum 26 may be an unobstructed vessel the function of which is to provide additional reaction time, or as described in more detail later, it may be provided with means to retain at least a part of the solid residue formed by the hydrogenation of the trace metal-containing oil. Ellluent from soaking drum 26 is withdrawn through line 27, passed through cooler 28 and line 29, and is discharged into gas separator 30. Hydrogen-containing gas from separator 30 is withdrawn through line 31 and at least a portion recycled through lines 32 and 22 by means of recycle gas compressor 33. The concentration of hydrogen in the recycle hydrogen stream is maintained at the desired value by purging a portion of the recycle gas through line 34 and adding make up hydrogen to the system through line 35. The liquid phase in gas separator 30 comprises a suspension of a solid residue in the treated oil and this liquid phase is withdrawn through line 36 and charged to decanter 37. Decanter 37 is a thickener which separates a claried oil from an oil of increased solid content and is lused to facilitate subsequent filtration. Clariiied oil from decanter 37 is withdrawn through line 38 and discharged to treated oil storage, not shown. Oil of increased solids content is withdrawn through line 39 and charged to filter 4l). Filtered oil from tilter 40 is ert material. If an inert packing is used in soaking drum 26, means for adding and removing the packing, not shown, are required. Addition and withdrawal of inert packing may be continuous during the operation of the process, or a multiple vessel system may be provided so that alternate soaking drums may be disconnected from the system to permit batch discharging and recharging of the packing. Similarly, the metals contained in the residue deposited upon the packing may be recovered by the means described in connection with metals recovery facilities 43.

The invention is further illustrated by the following examples:

EXAMPLE I In the series of tests of this example an oil containing trace metal components is treated in the presence of hydrogen under the conditions shown. The reaction vessel used in these tests is an unpacked reactor and the treated liquid and solid residue are withdrawn as a suspension and separated by liltration. Y

Table I lists laboratory tests on the trace metal-containing oils employed in this and the following examples. Table II lists operating data and product quality tests when applying this invention for the removal of trace metals from Mara Crude oil. Table III presents similar data obtained with San Ardo Crude oil. Table IV presents data obtained in applying the process of this invention to a vacuum distillate which contains trace metal components.

It will be noted that the process of this invention may be employed to remove substantially all of the vanadium contained in a heavy crude oil or a heavy vacuum' distillate. Essentially complete separation of vanadium is obtained with treated liquid recoveries as high as 96.0 weight percent of the feed oil.

Table I.-Feed stock quality tion with acid. The metal concentrate may then be proc- S H essed by chemical purification and reduction for recovery Crude I Crude 11 Agg, pagg, of the metal as indicated diagrammatically by line 44. 40 Crude Distillate As mentioned above soaking drum 26 may be provided with a means to retain at least a portion of the solid SirgvtisollPSE- 1% 18.5 residue formed in the hydrogenation of the trace metal- Visf es at 210 F 107.6 g5 contalning oil. Solid residue may be separated 1n soakmg As'lgpdlstlllatill, F2 426 drum 26 tfny Ipacking1 this (ii/essel vith an iiert Initerialii A 45 83; i .57g gig ortion o t e so i resi ue i site on t e ac D fe0- 4 p s BPO, p mg End pome..- 730 Cracked and to th1s extent the sollds separatlng load of decanter Vanadium, p.p.m- 100 37 and lter 40 is reduced. Suitable packings to retain INrer'mj: S a part of the solid residue are porcelain chips, steel turn- Carbon residue, percen ings, crushed petroleum coke, gravel, or other similar in- Table II.-Tests with Mara Crude1 Tosi' A B O D E F Operating conditions: i

Temperature, F 700 700 700 700 700 750 Pressure, p.s.i.g 685 1,000 1,500 2,000 l3,000 4.600 Hydrogen rate, eu. ttJbbl 142. 2 2. 2 169. 8 440. 0 657. 0 1, 073. 0 Yields, basis charge:

Treated liquid, weight percent 92 91. 8 95 94. 0 96. 0 90.0 Solid residue, weight percent. 4. 3 4. 3 5 5.0 3. 7 1. 0 Hydrogen consumption cu. ft./bbl 4.2 86. 2 76.8 293.0 290. 3 417. 0 Product quality: Treated oil- Gravity, API 30. 4 30. 9 30. 9 34. 6 34. 6 39. 8 vis., es., at F 3.72 t 11 3. 49 1.04 Vis., c.s., at 210 F-- 1.86 2. 0 1. 69 0. 9s ASTM distillation, F.:

IBP.- 150 10% rec` 302 230 50% rec. 556 440 V Eid point" 32 42 7 7 ana um. p.p.m 32 5. 0 0. 1 1.0 Nickel, p.p m 4 5 3 0.2 0. Iron, p.p.m. 0. 8 0. 8 4 0. 9 1. 0 Percent vanadium removal 86 81 86 97. 4 100 100 Solid residue:

Vanadium, p.p.m 2.000 1. 400 2, 400 4. 300 1l 600 Nickel, p.p.m 1. 200 1, 209 1,300 2,200 1,300 Iron, ppm r.. 3,200

1 Tests A, B, C, D, and E are made with Mara Crude I and Test F with Mara Crude II.

Test G H I Operating conditions:

Temperature, F 700 700 750 Pressure, p.s.i.g. 2, 000 5,000 4, 550 Hydrogen rate, cu. ft./bb 865.0 l, 5. 1, 175.0 Yields, basis charge:

Treated liquid, weight percent 91. 6 96. 3 82 Solid residue, weight pereent 1. 1. 5 1. 2 Hydrogen consumption, cu. it./b 565.0 639. 0 915.0 Product quality: Treated oil- Gravity, API 26. 4 22` 7 29. 3 Vis., c.s., at 130 F 9. 35 1. 93 Vis., ILS., at 210 F.. 3. 1. 05 ASTM distillation,

IBI 146 180 112 rec. 255 354 221 50% rec 529 649 447 E 750 760 760 Vanadium, ppm. 1. 0 5 0.3 Nickel, ppm- 7.0 12 4 Iron, p.p.m 0.6 1. 3 0.2 Percent vanadium remova 99 95 99. 7 Solid residue:

Vanadium, p.p.1n 6, 000 2, 100 1, 200 Nickel, p.p.m 2, 500 l, 100 2, 700 Iron, p.p.m 1, sco 2, 100 1, 700

Table IVI-Tesis with a heavy parayn distillate Test K L Operating conditions:

Temperature, F 700 750 Pressure, p.s.i.g 2,000 5,000 Hydrogen rate, cu. itJbbl 663.0 1, 105

Yields, basis charge:

Treated liquid, Weight percent 95.6 96 Solid residue, weight percent 3 2. 5 Hydrogen consumption ou. ft./bbl 253 410. 0 Product quality: Treated oil- Gravity, API 27 4 33. 1 Vis., c.s., at 130 F 3.12 Vis., c.s., at 210 F 1.62 ASTM distillation, F.:

IBP 146 128 365 258 755 581 760+ 760+ Vanadium, p.p.r.n 0. 5 0.7 Nick 0. 5 0. 02 Iron, p.p.m 3.0 0. 9 Percent vanadium removal 99 98 Solid residue:

Vanadium, p.p.m 1, 400 1, 400 Nickel, p.p.m 3, 000 850 EXAMPLE II In another series of tests, oils containing trace metal components are treated in the manner used in Example I except that hydrogen is neither admixed with nor included in the feed stock. Data for these tests are given in Table V.

It will be noted that treatment of metal-containing oils Table V.-Tests in absence of added hydrogen Test M N O Feed Stock (See Table I) Mara Crude I San Ardo Crude Operating conditions:

Temperature, F 700 700 750 Pressure, p.s.i.g 270 2, 000 3, 000 Yields, basis charge:

Treated liquid, weight percent 78. 5 73. 6 84 Solid residue,weight percent 6.5 12. 6 7 Product quality: Treated oilravity, API 32.2 22. 1 20. 3 Vis c s., at F 2. 78 6. 14 Vis c s., at 210 F 1.42 2. 43 ASTM distillation, F

IBP 240 206 10% rec 294 284 301 50% rec-- 528 i 516 568 End point- 724 738 742 Vanadium, p.p.m 20 6 19 Nickel, p.p.m 2 5 19 Iron, p.p.m 0.. 7 3 0. 4 Percent vanadium removal 91.. 0 94 EXAMPLE III In another series of tests Mara Crude oil is heated with hydrogen and passed through a soakingl drum in which an inert packing is disposed. In this method of processing a major portion of the solid residue formed is retained by the inert packing. `Only that portion of the solid residue not retained by the packing in the soaking drum appears as a suspension in the treated liquid. The solid residue remaining in the treated oil is separated by filtration and combined with the fouled packing removed from the soaking drum at the conclusion of the test for recovery of the metals contained therein. The operating conditions and results of this series of tests are given in Table VI.

Comparison of the results obtained with an inert packing as used in this example with the data of Example I where an unpacked reactor was used indicates that this method of operation is equally satisfactory as a means of removing metallic components. Furthermore, this method of operation permits the separation of a substantial amount of the metal-containing solid residue by retention with an inert packing.

Table Vil-Tesis employing inert packing in a soaking drum Test- P Q R S T U V W X Feed Stock (See Table I) Mara Crude I inert Beckman- (l) (l) (l) (l) (l) (l) (l) (2) (2) Operating condltions:

Temperature, F 800 830 835 845 850 850 835 850 Pressure, p.s.i.g- 2, 500 2, 500 2, 500 2, 500 2, 500' 2, 500 2, 500 2, 500 Hydrogen, rate, eu. ft./bbl 365. 0 438. 5 657.0 990. 0 920. 4 682.7 448.0 Oil residence time, min 7 7 7 7 7 7 7 7 Yields, basis charge:

Treated liquid, Weight percent 96 94 90.6 90. 0 90.9 89.1 88. 9 94.6 89. 3 Solid residue, Weight percent 2. 3 3.4 2. 3 2.0 2. 6 1. 3 4. 1 Hydrogen consumption cu. ft./bbl 245. 2 291.0 660.0 396. 6 339.. 9 373 256.0 Product quality: Treated oil- Gravity, API 29.0 30. 6 35. 1 35, 2 35. 8 35. 9 33.4 34 6 33. S Carbon residue, percent.. 7. 3 5.0 3. 5 2.1 1. 8 3. 3 Vanadium, p.p.n1 190 140 27 23 6 2 35 36 4l Nickel, ppm.. 17 12 2 2 1 0.6 2 2. 4 3 Iron, p.p.m 7 1 20. 1 0.3 0 1 0.3 0.. 3 0.4 20. 1 Percent vanadium removal-. 13 36 88 89 97 99 84 84 82 Solid residue:

Vanadium, p.p rn 4, 200 3, 600 4, 400 4, 300 4, 400 3,200 Nickel, 11.11.111.-. 940 780 2, 300 1,200 670 Iron, p.p.m 1, 800

1 Berl saddles. 2 Steel turnings.

Obviously many modifications and variations of the indeparting from the spirit and scope thereof and only Vsuch limitations should be imposed as are indicated in the appended claims.

We claim:

1. The method of treating a petroleum oil containing trace metal components for the separation of said components which comprises contacting said oil in the absence of a catalyst with hydrogen at a hydrogen feed rate of from about 438.5 cubic feet to about 1585 cubic feet per barrel of said petroleum oil and at a temperature of 700 to 850 F. and a pressure of 2000 to 5000 p.s.i.g. to react at least a portion of said hydrogen with `a component of said oil to produce a treated oil of reduced metal content and a solid metal-containing residue and separating said treated oil from said reidue.

2. The method of claim 1 in which said hydrogen and said oil are contacted in the presence of a contact m-aterial consisting essentially of an inert non-catalytic packing material.

3. AV method for removing vanadium and other trace metal components from a petroleum oil containing same which method comprises converting saidV petroleum oil into a liquid phase substatially free from such metal components and a solid residue phase containing most of said metal components by non-catalytically reacting said petroleum oil with hydrogen in la reaction zone at a temperature of 70 to 850 F., a pressure of 2000 to 5000 p.s.i.g., and a hydrogen feed rate within the range of from -about 438.5 cubic feet to about 1585 cubic feet per barrel of petroleum oil, withdrawing said liquid phase and said solid phase from said reaction zone and then separating said solid phase from said liquid phase.

4. A method in accordance with claim 3, wherein said reaction is carried out in an unpacked reaction zone.

5. A method in accordance with claim 3, wherein said reaction zone is packed with an inert non-catalytic solid packing material and wherein said packing material retains part of said solid residue thereon.

6. A method in accordance with claim 5, wherein said solid packing material is selected from the group consisting of berl saddles, steel turnings, porcelain chips and crushed petroleum coke.

.7. A method as claimed in claim 3, wherein the hydrogen feed rate is within the range of from about 657 cubic feet to yabout 1175 cubic feet per barrel of said petroleum oil.

8. A method as claimed in claim 3, wherein hydrogen is consumed in said reaction in an amount within the range of from about 290 cubic feet to about 915 cubic feet per barrel of said petroleum oil.

References Cited in the file of this patent UNITED STATES PATENTS 2,730,487 Porter et al. Ian. 10, 1956 2,758,060 Porter et al Aug. 7, 1956 2,754,525 Porter et al. Sept. 25, 1956 FOREIGN PATENTS 682,387 Great Britain Nov. l2, 1952 517,222 Belgium Feb. 14, 1953 1,064,703 France Dec. 30, 1953 UNITED STATES PATENT oEFICE CERTIFICATE 0E CORRECTION Patent Nen 2&910 1,434 I October E?, 1959 Howard V Heee et eL,

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the seid Letters y Patent should read as corrected below.

column '79 time 3c for "'70 te eric@ EL," e 70e te 85e@ tu me Signed and sealed this 10th day et? Mey 1960.,

(SEAL) Attest:

KARL ILAXLNE HUBERT Cn WTSN Attesting Officer Commissioner ot Patents 

1. THE METHOD OF TREATING A PETROLEUM OL CONTAINING TRACE METAL COMPONENTS FOR THE SEPARATION OF SAID COMPONENTS WHICH COMPRISES CONTACTING SAID OIL IN THE ABSENCE OF A CATALYST WITH HYDROGEN AT A HYDROGEN FEED RATE OF FROM ABOUT 438.5 CUBIC FEET TO ABOUT 1585 CUBIC FEET PER BARREL OF ASID PETROLEUM OIL AND AT A TEMPERATURE 